TW201500202A - Resin laminate - Google Patents

Abstract

The present invention provides a resin laminate with high surface hardness and high transparency. The present resin laminate, which comprises a hard resin layer formed by a curable resin composition having a multifunctional (meth)acrylate monomer as main component and having a three dimension crosslink structure and a thickness equal to or higher than 25 μ m and equal to or less than 250 μ m, and a substrate layer constructed by monolayer or a plurality of layers of a thermoplastic resin, is characterized that by the hard resin layer has a single tension elasticity of 2,000 to 4000 MPa and a full-spectrum transparency of 90% or more, also, the ratio of total thickness of the substrate layer t1 to the thickness of the hard resin layer t2 (t1 / t2) is equal to or higher than 0.25 and equal to or less than 10, the Bierbaum scratch hardness of the resin laminate is equal to or higher than 20 kg/mm<SP>2</SP> and equal to or less than 700 kg/mm<SP>2</SP>.

Description

Resin laminate

The present invention relates to a resin laminate having excellent surface hardness, transparency, and moldability, and particularly to a resin laminate which is applied to a display panel as a transparent multilayer sheet.

In an electronic device such as a digital camera or a mobile phone, an acrylic resin, a polycarbonate, or a polyparaphenylene can be used as a substrate such as a liquid crystal display or a protective film for protecting a surface of a liquid crystal display or the like from damage or contamination. A laminate made of a thermoplastic resin such as ethylene dicarboxylate. The resin which forms these laminated bodies has the characteristics of favorable optical characteristics and is less likely to be broken than glass, and has been widely used in the field of conventional glass use in recent years. However, thermoplastic resins such as acrylic resin, polycarbonate, and polyethylene terephthalate have disadvantages such as poor surface hardness, abrasion resistance, and scratch resistance as compared with glass, and are easily scratched.

In order to solve this drawback, the surface modification of the resin laminate has been studied in the past. For example, it has been widely applied to the surface of a substrate to apply a thermosetting resin or an ultraviolet curable resin. In the resin laminated body to which the coating is applied, although the abrasion resistance and the scratch resistance are improved to some extent, the surface hardness is still insufficient, and the surface hardness is low as compared with the glass, and there is a big problem in practical use. .

For the transparent plastic material, as a coating technique for further improving the surface hardness, for example, it is attempted to incorporate a filler having a high hardness into the hard coat layer to improve the surface hardness (refer to Patent Document 1, Patent Document 2, and Patent Document 3). . Further, as a similar method, the film thickness of the hard coat layer is increased, and in order to alleviate the generated stress, inorganic and/or organic crosslinked particles are mixed, or a functional group is introduced on the surface of the particle, and the resin of the hard coat layer is partially partially Crosslinking is carried out to study a method of mixing organic and inorganic materials (refer to Patent Document 4 and Patent Document 5). Further, by multilayering the hard coat layer and increasing the thickness of the entire coating layer, it is attempted to obtain a higher surface hardness (refer to Patent Document 6).

However, as a specific example of such methods, a polyethylene terephthalate or a cellulose triacetate film having a higher pencil hardness than a polycarbonate resin is used as a substrate, and a pencil is obtained. The hardness is 4H to 6H, and the effect is verified, but the pencil hardness cannot be achieved only with a thin hard coat layer, and a hard base layer or an auxiliary function of an inorganic material is required. Therefore, these underlayers and inorganic materials are the main factors that hinder transparency, and are not suitable as display devices such as liquid crystal displays.

Also, try to use a polycarbonate resin of a resin having a low pencil hardness, and contain a difunctional urethane acrylate, a polyfunctional oligo, a polyfunctional monomer, a monofunctional monomer, and a specific functional group. A coating film composed of a base number of the ultraviolet curable resin is formed into two layers on a polycarbonate resin substrate with a specific film thickness. In this technique, the pencil hardness is at most 4H, which is still insufficient (refer to Patent Document 7).

Further, the above Patent Document 7 is evaluated by the scratch hardness of the pencil method according to JIS K 5600-5-4, but is accumulated on the thermoplastic resin layer. The hard coat layer and the hard resin layer are the properties or thickness of the thermoplastic resin and the hard resin layer, which are affected by the thermoplastic resin of the lower layer, and the plastic deformation and elastic deformation due to the dent are difficult to see at a glance. Is it a dent or a scratch due to scratching. Further, depending on the material of the hard resin layer, cracks may occur due to deformation of the dents which are not originally thought, and it is difficult to accurately measure the surface hardness only by the pencil hardness. In addition, when it is used for the use of a protective sheet such as a liquid crystal display as described above, it is necessary to consider the protection against scratches caused by stronger metals or minerals in daily life, and is softer than metal or mineral. In the judgment by the pencil method, it may be deviated from the abrasion resistance and scratch resistance of the actual daily life.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-107503

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2002-060526

[Patent Document 3] WO2010/035764 manual

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2000-112379

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2000-103887

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2000-052472

[Patent Document 7] Japanese Laid-Open Patent No. 4246643

The present invention has been made in view of the problems of the above conventional techniques, and provides a resin product having high surface hardness and high transparency. Layer body.

In order to obtain a resin laminate having excellent surface hardness and high transparency, the present inventors have found that a resin having a hard resin layer composed of a specific curable composition and a base material layer composed of a thermoplastic resin has been found. The laminate can be achieved at the same time, thus completing the present invention.

In other words, the present invention comprises a hard resin having a three-dimensional crosslinked structure and having a thickness of 25 μm or more and 250 μm or less, which is formed of a curable resin composition containing a polyfunctional (meth)acrylic monomer as an essential component. a resin laminate of a base layer composed of a single layer or a plurality of layers of a thermoplastic resin; characterized in that the hard resin layer alone has a tensile modulus of 2000 to 4000 MPa and a total light transmittance. 90% or more, the thickness t and the total thickness t of the substrate layer ₁ and a hard resin layer is smaller than (t ₁ / t _{2) 2} of 10 or less is 0.25 or more, Bill Bam resin laminate (Bierbaum) scratch hardness A resin laminate of 20 kg/mm ² or more and 700 kg/mm ² or less.

Here, the evaluation of the scratch hardness of the resin laminate of the present invention is the scratch hardness according to the evaluation method of ASTM D1526-58T. This method is an evaluation method in which the shape of the pressure is an acute angle and a low load, so that the properties of the upper hard resin layer and the lower thermoplastic resin are not affected by the thickness, and the evaluation as a laminate is not uniform and can be performed. Evaluation of hardness.

In the present invention, the number of functional groups of the (meth)acrylic monomer in the curable resin composition forming the hard resin layer is preferably 4 or more, and the solid content of the curable resin composition is contained per 100 g. A ratio of 40g or more.

Further, in the present invention, it is preferable that the hard resin layer and the base material layer are laminated on each other. The adhesive layer is one or more selected from the group consisting of an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive. Further, the hard resin layer and the thermoplastic resin layer may be laminated via an easy-adhesion layer. Furthermore, in the present invention, a hard resin layer may be provided on both the front and back sides of the base material layer.

Further, in the present invention, the polyfunctional (meth)acrylic monomer contained in the curable resin composition forming the hard resin layer is preferably a caged silsesquioxane structure. More preferably, the polyfunctional (meth)acrylic monomer having a cage sesquiterpene structure is represented by the following formula (1).

(R ¹ SiO _3/2 ) _n (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1)

(wherein R ¹ to R ⁶ represent an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group or an oxirane ring; The bases may each be the same group, or may contain different groups having at least two (meth)acrylic groups, and n, m, and l are average values, n is a number from 6 to 14, and m is 0. A number of 4, l is a number from 0 to 4, and satisfies m≦1.)

The resin laminated system of the present invention can maintain transparency and have high surface hardness. Further, since a resin laminated body which is sufficiently resistant to impact or bending can be formed, it can be used as a frame body which is excellent in workability such as molding, cutting, punching, and the like, and which is excellent in display panel or design.

1‧‧‧hard resin layer

2‧‧‧Bonded layer

3‧‧‧Substrate layer

3b‧‧‧ substrate layer

4‧‧‧Printing layer

5‧‧‧ Pressure-sensitive adhesive layer

Fig. 1 is a schematic view showing the laminated body of the first aspect of the invention.

Fig. 2 is a schematic view showing the laminated body of the second aspect of the invention.

Fig. 3 is a schematic view showing the laminated body of the third aspect of the invention.

Figure 4 is a schematic illustration showing the use of the pressure used in the Birbam scratch test method.

Hereinafter, the present invention will be described in detail.

<hard resin layer>

The curable resin composition in which the hard resin layer is formed in the resin laminate of the present invention is not particularly limited as long as it contains a polyfunctional (meth)acrylate having two or more ethylenically unsaturated bonds in the molecule. limit. That is, as the above polyfunctional (meth) acrylate, for example, a difunctional (meth) acrylate or a trifunctional or higher (meth) acrylate.

Among them, as a difunctional (meth) acrylate, for example, ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, hexane diol (meth) acrylate, long-chain fat Group II (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate Ester, propylene glycol (meth) acrylate, glycerol (meth) acrylate, triethylene glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, di(meth)acrylic acid bicyclic Amyl ester, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, triglycerol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di Methyl) acrylate, allylic cyclohexyl (meth) acrylate, methoxylated cyclohexyl (meth) acrylate, acrylated isocyanurate, bis(acryloxy) Pentanediol) adipate, bisphenol A di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, bisphenol S di(meth)acrylate, butanediol di(a) Acrylate, bis(meth) acrylate, di(meth) acrylate, zinc di(meth) acrylate, and the like.

Further, as a trifunctional or higher (meth) acrylate, for example, trimethylolpropane tri(meth) acrylate, trimethylolethane tri(meth) acrylate, glycerin tri(methyl) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tris(meth)acrylate, tris(propylene oxy) Ethyl)isocyanurate, tris(methacryloxyethyl)isocyanate,pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylol Propane tetraacrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate , alkyl modified dipentaerythritol penta (meth) acrylate, carboxylic acid modified dipentaerythritol penta (meth) acrylate, urethane tris (meth) acrylate, ester tri (meth) acrylate , urethane hexa(methyl) Acrylate, ester hexa(meth) acrylate, and the like.

These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

Further, as the curable resin composition, a compound having a structure having a curable cage type sesquiterpene oxide is preferable as the polyfunctional (meth)acrylic monomer.

In addition, the compound having a structure of a curable cage type sesquiterpene oxide is more preferably a cage type sesquiterpene oxide resin represented by the following general formula (1).

(R ¹ SiO _3/2 ) _n (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1)

(wherein R ¹ to R ⁶ represent an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group or an oxirane ring; The bases may each be the same group, or may contain different groups. The formula (1) has at least two (meth)acrylic groups, and n, m, and l are average values, and n is a number of 6 to 14. m is a number from 0 to 4, l is a number from 0 to 4, and satisfies m≦1.)

The above-mentioned cage type sesquiterpene oxide resin is a reactive functional group composed of a (meth)acrylic group-containing organic functional group or a (meth)acryloxyalkyl group, and has a molecular weight distribution and A cage type sesquiterpene oxide resin having a controlled molecular structure is preferred, and a part thereof may be substituted by an alkyl group, a phenyl group or the like, and is not a completely closed polyhedral structure, and may be a partially cleaved structure. In the case of a partially cleaved structure, the linked polyfluorene chain may also have a (meth)acrylic group.

Moreover, the hardened resin composition used in the present invention is The hard resin layer to be formed must have a thickness of 25 μm or more and 250 μm or less. When the thickness is less than 25 μm, sufficient scratch hardness cannot be obtained. When the thickness exceeds 250 μm, the total light transmittance is low, and there is a problem that transparency required for a display or the like cannot be obtained.

Further, the monomer of the hard resin layer used in the present invention has a tensile modulus of from 2,000 to 4,000 MPa. When the tensile modulus is less than 2,000 MPa, the scratch hardness of the resin laminate is less than 20 kg/mm ² , and when it exceeds 4,000 MPa, the workability such as molding and cutting becomes difficult. Further, the hard resin layer used in the present invention has a total light transmittance of 90% or more since it is suitable for a display panel or the like.

In addition, the number of functional groups of the (meth)acrylic monomer of the curable resin composition forming the hard resin layer is 4 or more, and the solid content of 100 g of the curable resin composition is preferably 40 g or more. . When the number of functional groups of the (meth)acrylic monomer is 4 or more and less than 40 g, even if the thickness is 25 μm or more, there is a problem that sufficient scratch hardness cannot be obtained.

In addition, as for the resin-based layered product, it is preferable that the solid content of the curable resin composition is obtained from the viewpoint of obtaining a sufficient scratch hardness and performing machining such as cutting or punching. The molar number of 100 g of the (meth)acryl group is in the range of 0.6 to 0.9. Here, the molar number of the (meth)acrylic group per 100 g of the solid content of the curable resin composition is calculated by the following formula.

(molar number per 100 g of (meth)acrylic group) = (100 / molecular weight) × 1 number of (meth)acrylic groups in the molecule In addition, when a plurality of polyfunctional (meth) acrylates are used as the curable resin composition, the average number of moles of (meth)acrylic groups calculated by the blending ratio is used, and yttrium oxide or the like is blended. The weight is also included in the filler, and the average value of the number of moles of the (meth)acryl group is calculated.

Further, the hard resin layer composed of the curable resin composition, and the number of moles of the (meth)acrylic group per 100 g of the solid content of the curable resin composition may be in the range of not less than 0.6 to 0.9. Functional group (meth) acrylate combination. However, when a certain amount or more of a monofunctional (meth) acrylate is blended, the surface hardness is low, and when it is adjusted for the purpose of adjusting the viscosity, etc., it is desirable to be kept to a minimum and compared with the curable resin composition. Preferably it is 30% by weight or less.

Here, as the monofunctional (meth) acrylate, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dibutyl acrylate, butyl acrylate, amyl acrylate, acrylic acid Neopentyl ester, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, hydrazine acrylate Ester, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, isotetradecyl acrylate, cetyl acrylate, Acetyl decyl acrylate, octadecyl acrylate, decyl acrylate, eicosanyl acrylate, n-lauryl acrylate, stearyl acrylate, etc., alkyl acrylate, propylene morpholine, cyclohexyl acrylate, Dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxy acrylate Ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-phenoxypropyl acrylate, 1,4-butanediol monoacrylate, 2-hydroxyalkyl propylene decyl phosphate, 4-hydroxycyclohexyl acrylate, 1,6-hexanediol monoacrylate, neopentyl glycol monoacrylate, and a cyclic ester compound such as ε-caprolactone added to the hydroxy group-containing acrylate compound a compound obtained by an addition reaction of a glycidyl ether-containing compound such as an alkyl epoxidized propyl ether, an allyl epoxidized propyl ether or a epoxypropyl acrylate with acrylic acid, or a polyethylene glycol Monoacrylate, polypropylene glycol monoacrylate, tetrahydrofuran acrylate, decyl acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl acrylate, acrylic acid (2-Isobutyl-2-methyl-1,3-dioxolan-4-yl)methyl ester or the like.

The curable resin composition used in the present invention is obtained by radical copolymerization to obtain a (meth)acrylic resin copolymer. In order to improve the physical properties of the (meth)acrylic resin copolymer or to promote radical copolymerization and the like, various additives may be blended in the curable resin composition of the present invention. The additive for promoting the reaction may, for example, be a thermal polymerization initiator, a thermal polymerization-promoting initiator, a photopolymerization initiator, a photoinitiator, a sensitizer or the like. When the photopolymerization initiator or the thermal polymerization initiator is blended, the amount thereof to be added may be in the range of 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by total of the total of the hardening type resin composition. range. When the amount is less than 0.1 part by weight, the curing is insufficient, and the strength and rigidity of the obtained hard resin layer are lowered. On the other hand, when it exceeds 5 parts by weight, problems such as coloring of the hard resin layer may occur.

When the hardened resin composition is used as a photocurable composition As the photopolymerization initiator to be used, a compound such as a benzophenone-based, a benzoin-based, a diphenylketone-based, a thioxanthone-based or a mercaptophosphine-based oxide can be suitably used. More specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1 can be exemplified -Phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propan-1-one, 2-hydroxy-1-[ 4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl]-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester , 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)phenyl-phosphine oxide, 1,2-octane Diketone, 1-[4-(phenylthio)-, 2-(0-benzylidenehydrazide), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) )-9H-carbazol-3-yl]-,1-(0-ethylindenyl), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholinylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl)-butanone-1-one, bis-2,6-dimethoxybenzhydryl-2,4,4-trimethylpentylphosphine oxide, diphenyl ketone , thioxanthone, 2-chlorothiazepinone, 2,4-diethylthiazinone, isopropyl thioxanthone, 1-chloro-4-propoxy The thioxanthone may be used alone or in combination of two or more.

The curable resin composition used in the present invention is prepared by blending a radical polymerization initiator with heat or light irradiation to produce a hard resin layer having an arbitrary shape such as a flat surface or a curved surface. When a hard resin layer having an arbitrary shape is produced by heating, the molding temperature can be selected from the range of room temperature to about 200 ° C depending on the selection of the thermal polymerization initiator and the accelerator. At this time, it is polymerized and cured in a mold or a steel strip to obtain a hard resin layer having a desired shape.

Further, when the hard resin layer is produced by light irradiation, it can be obtained by irradiating ultraviolet rays having a wavelength of 10 to 400 nm or visible light having a wavelength of 400 to 700 nm. The wavelength of light used is not particularly limited, but it is particularly suitable to use near ultraviolet rays having a wavelength of 200 to 400 nm. A lamp used as a source of ultraviolet light, such as a low pressure mercury lamp (output: 0.4 to 4 W/cm), a high pressure mercury lamp (40 to 160 W/cm), an ultrahigh pressure mercury lamp (173 to 435 W/cm), a metal halide lamp (80 to 160 W/cm), pulsed xenon lamp (80 to 120 W/cm), electrodeless discharge lamp (80 to 120 W/cm), and the like. These ultraviolet lamps are characterized by various spectral distributions depending on the type of photoinitiator used.

A method of obtaining a hard resin layer having an arbitrary shape used in the present invention by light irradiation, for example, a mold having a transparent cavity shape and having a transparent material such as quartz glass, is injected into the mold, and the hardenable resin composition is injected as described above. A method in which an ultraviolet lamp is irradiated with ultraviolet rays, polymerized and cured, and released from a mold to produce a hard resin layer having a desired shape; or when a mold is not used, for example, a moving steel strip is coated with a doctor blade or a roller coater. In the curable resin composition of the present invention, the ultraviolet light is irradiated with ultraviolet rays to polymerize and cure the film, and a method of producing a sheet-like hard resin layer.

<Substrate layer>

As the substrate layer of the present invention, transparency is desired, and polyethylene terephthalate (PET), triethylenesulfonyl cellulose (TAC), polyethylene naphthalate (PEN), and the like can be suitably used. Polymethyl methacrylate (PMMA), polycarbonate (PC), polyimine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC) , cyclic olefin copolymer (COC), decene-containing resin, polyether oxime, cellophane, aromatic polyfluorene Various resin films such as amines. These films can be used without extension or by those who have implemented extension processing. Among these, polyethylene terephthalate (PET) and polymethyl methacrylate are particularly preferable from the viewpoints of heat resistance, transparency, weather resistance, solvent resistance, impact resistance, workability, and cost. Ester (PMMA), polycarbonate (PC).

The base material layer imparts rigidity to the resin laminated body of the present invention, and imparts sufficient resistance to impact or bending. For example, the hard fat resin layer of the present invention is formed of a curable resin composition containing a polyfunctional (meth)acrylic monomer having a cage sesquiterpene structure, and can be suitably provided with a high scratch hardness. Although the surface hardness is set to 250 μm or less in order to ensure transparency, the impact resistance is insufficient. Therefore, in the present invention, the base material layer is sufficiently resistant to impact or bending. The base layer has a total thickness of from 0.5 to 2000 μm, preferably from 10 to 1000 μm. When it is less than 0.5 μm, sufficient rigidity cannot be obtained, and when it exceeds 2000 μm, processing such as molding, cutting, or punching becomes difficult. Further, the total thickness of the present invention, the base layer is t ₁ t ratio of the thickness of the rigid resin layer ₂ of (t ₁ / t ₂₎ is 0.25 or more 10 or less. When the ratio of the thickness is less than 0.25, the workability such as forming, cutting, or punching becomes difficult. When the ratio exceeds 10, the Birkbam scratch hardness is less than 20 kg/mm ² .

<Next layer>

In the resin laminate of the present invention, the hard resin layer and the substrate layer can be laminated by any of a film-like or sheet-like adhesive layer (adhesion layer).

As the adhesive layer, the thickness thereof is from 0.1 to 30 μm, preferably from 0.1 to 10 μm. When it is less than 0.01μm, it is difficult to obtain sufficient effect When the thickness is 30 μm or more, the scratch hardness of the laminated body may not be sufficiently obtained.

Further, as the adhesive layer constituting the adhesive layer, an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive can be used. As such, for example, an acrylic adhesive, an urethane adhesive, an epoxy adhesive, a polyester adhesive, a polyvinyl alcohol adhesive, a polyolefin adhesive, a modified polyolefin adhesive, a polyvinyl alkyl ether. Adhesive, rubber adhesive, chlorinated ethylene/vinyl acetate adhesive, styrene/butadiene/styrene copolymer (SBS copolymer) adhesive, hydride (SEBS copolymer) adhesive, ethylene/acetic acid Vinyl ester copolymer, ethylene-styrene copolymer and other ethylene binder, ethylene/methyl methacrylate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/ethyl acrylate copolymer The acrylate adhesive or the like is not particularly limited as long as it is excellent in adhesion, transparency, and workability.

<easy layer>

Further, as the other member constituting the adhesive layer, for example, the layer is easily adhered. The easy-to-adhere layer is applied to the surface of the resin which is difficult to bond, and is subjected to a layer which is chemically easy to handle or physically easy to handle. Here, the chemical property is easily followed by a film layer in which a resin having a functional group is formed on a substrate layer in detail, and a chemical bond is formed with a hard resin layer to obtain an adhesive force, and on the other hand, a physical easy adhesion ability is obtained. It means that a resin film layer or an inorganic film layer having irregularities is formed on a base material layer, and an adhesion force is obtained by an anchoring effect. As a material having chemically apt to be able to be used, for example, a polyfunctional (meth) acrylate, an epoxy, a thiol group-containing compound, or the like, as a material having physical susceptibility, for example, SiO ₂ , SiN, A vapor deposition film such as SiC.

Fig. 1 shows a first aspect of the resin laminate of the present invention. The resin laminate shown in Fig. 1 is obtained by sandwiching the adhesive layer 2 on both surfaces of a base material layer 3 made of a thermoplastic resin, and a hard resin layer 1 on the upper and lower sides thereof. Further, in the resin laminate of the first aspect, the hard resin layer 1 on one side has a structure in which the printed layer 4 is formed. Here, the adhesive layer 2 functions as an adhesive layer for integrating the hard resin layer 1 and the base material layer 3 . Further, on the lower surface of the resin laminated body of the present invention, a pattern, a character, or the like can be formed by forming the printed layer 4. The printed pattern as the printed layer 4 can be arbitrarily selected, for example, wood grain, stone grain, cloth grain, sand grain, geometric pattern, letter, all solid, metal, and the like. Furthermore, the adhesive layer 2 here may be the aforementioned adhesive layer or easy adhesive layer.

It is preferable to mix the resin component with the hard resin layer or the base material layer in the printing layer 4, for example, a polyvinyl-based resin such as a chlorinated ethylene/vinyl acetate copolymer, a polyamine-based resin, or a poly Ester resin, acrylic resin, polyurethane resin, polyvinyl formal resin, polyester urethane resin, cellulose ester resin, alkyd resin and chlorinated polyolefin resin . By blending such a resin component, peeling or peeling of printing can be suppressed.

Further, when the printing layer 4 is formed, a coloring agent containing a pigment or a dye of an appropriate color can be used.

As a method of forming the printing layer 4, for example, a printing method such as an offset printing method, a gravure wheel transfer method, or a screen printing method, a coating method such as a roll coating method or a spray coating method, and a flexographic printing method.

As the thickness of the printed layer 4, an appropriate thickness may be selected so as to obtain a desired surface appearance in the resin laminate, and is usually about 0.5 to 30 μm.

Further, in the resin laminate of the present invention, the structures shown in Figs. 2 and 3 can be exemplified in the second and third embodiments.

In the second embodiment shown in Fig. 2, the printed layer 4 is formed on the upper surface of the base material layer 3b, and the pressure-sensitive adhesive layer 5 is interposed between the upper portion on the side of the printed layer 4 and the side on which the printed layer 4 is not formed. The hard resin layer 1 is formed on the side of the printing layer 4, and the substrate layer 3 is formed on the side where the printing layer 4 is not formed.

In the second embodiment, the base material layer 3b to be used is not particularly limited as long as it is transparent, and polymethyl methacrylate (PMMA) is preferred.

Further, in the third embodiment shown in Fig. 3, the hard resin layer 1 is formed on the upper surface of the base material layer 3 via the adhesive layer 2, and the printed layer 4 is formed on the lower surface of the base material layer 3, The second base material layer 3 is formed on the lower portion via the pressure-sensitive adhesive layer 5.

A pressure-sensitive adhesive layer 5 which is used in the embodiment of the second and third embodiments can be a known pressure-sensitive adhesive. Specifically, an adhesive such as a natural rubber-based resin, a synthetic rubber-based resin, a polyoxynated resin, an acrylic resin, a vinyl acetate-based resin, or a urethane-based resin can be used.

The above-mentioned adhesive agent is not particularly limited as long as it can provide desired light transmittance, adhesiveness, and weather resistance. Further, in order to prevent deterioration of the pigment by the constitution of the layer, it is desirable that the adhesive contains suction. A UV absorber (benzotriazole, etc.) that absorbs ultraviolet rays.

As the pressure-sensitive adhesive layer 5, the average thickness thereof is from 0.01 to 30 μm, preferably from 0.1 to 10 μm. When it is less than 0.01 μm, sufficient bonding strength cannot be obtained, and unevenness of the printed layer is absorbed, and the effect of planarization is also lowered. Further, when it exceeds 30 μm, the main cause of the scratch hardness of the laminated body is lowered.

In the first and third embodiments of the present invention, the three-dimensional shape can be imparted by thermoforming in the state of the resin laminate. The base material layer 3 of FIGS. 1 and 3 can be formed by heat, and the hard fat resin layer 1 can have an excellent flexibility, can follow the shape of the base material layer 3, and can be an integrally molded product via the adhesive layer 2. Examples of the hot forming include vacuum forming, air pressure forming, press forming, and the like.

Further, in the layer configuration of the resin laminate shown in Fig. 2 of the embodiment of the present invention, A-parts (hard resin layer 1, pressure-sensitive adhesive layer 5, and printed layer 4) which are previously formed into a specific shape are formed in advance. The base material layer 3b) and the B component (pressure-sensitive adhesive layer 5, base material layer 3) are bonded together via the pressure-sensitive adhesive layer 5, or the base material layer 3 constituting the B component is preliminarily subjected to A. After the part-forming pressure-sensitive adhesive layer 5 is loaded into a mold having a desired shape, it is formed by injection molding and injection molding as a resin for injection molding.

Further, in the first to third embodiments of the embodiment, the printed layer 4 is formed. However, the printed layer 4 may be omitted, and any one of the layers may be formed by any printing method as long as it conforms to the manufacturing step of the laminated body.

When the molded base material layer 3 is injected, it is preferable to use a thermoplastic resin for injection molding to have transparency, and it is suitable to use polyethylene terephthalate. Ester (PET), triethyl fluorenyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimine (PI) , polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cyclic olefin copolymer (COC), decene-containing resin, polyether oxime, cellophane ), various resin films such as aromatic polyamines. From the viewpoints of heat resistance, transparency, weather resistance, solvent resistance, rigidity, and cost, polyethylene terephthalate or polycarbonate is preferred, and polycarbonate is particularly preferred from the viewpoint of impact resistance.

Here, a method of evaluating the hardness of the present invention will be described. At ASTM D 1526-58T, a method for determining the Birerbaum scratch hardness using a tip having an acute angled shape is disclosed. This method is a method in which a certain load is applied, and the sample is directly moved in a state where the surface of the sample is pressed against the pressure, and the hardness is evaluated by the width and load of the flaw of the pressure. The inventors of the present invention used this method to perform hardness evaluation on various materials, and as a result, it was found that the pencil hardness can more accurately determine the unsearable scratch resistance, and the characteristics of the material at this time are examined. That is, the Bilbaum scratch hardness is preferably in the range of 20 to 700 kg/mm ² . If the value is smaller than this range, it is easy to scratch due to the small load, so it is not preferable. If it is larger than the value of this range, it is easy to have a small scratch, which is not preferable. In addition, when the value of the scratch hardness is large, the width of the flaw is measured in the measurement of the scratch hardness of the Bilbaum. However, the larger the value, the smaller the damage is, even if the load is small, it is presumed that for the hard pressure. No resistance, so the surface is damaged and the person is scratched. Conversely, when investigating a small load, the material that absorbs the pressure generated by the pressure without scratching is actually a surface hardness. From these investigations, the preferred Bilbaum scratch hardness ranges from 30 to 600 kg/mm ² , more preferably from 40 to 500 kg/mm ² . Further, the load at the Birbam scratch hardness is measured, and a suitable load is selected in the range of several g to several tens of g. If the load is small, it is impossible to measure because there is no scratch, and if it is too large, it is difficult to discriminate the difference, so it is not good. Furthermore, the material which is not scratched in the range of the load has the same meaning as the processing difficulty, and is therefore not preferable.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. Furthermore, the evaluation methods and symbols used in the present invention are as follows.

1) Scratch hardness: according to ASTM D 1526-58T (Bilbaum scratch test method for plastic materials), a triangular pyramid formed by three triangles whose front end is made of diamond and has an apex with an internal angle of 90 degrees The front end shaped press (Fig. 4) was placed so that the bottom edge of one triangular cone was perpendicular to the traveling direction, and the test was carried out at a load of 30 g. The scratch was visually observed by a microscope observation, and the width of the test mark was measured.

2) Total light transmittance: measured according to JIS K 7361-1

3) Film thickness: measured by Mitutoyo ID-SX

4) Tensile modulus: measured according to JIS 7127

5) Machinability: In the path processing machine (manufactured by Megaro Technica Co., Ltd.), the path knife (manufactured by Neiyama Blade, 2 mm, straight edge) was attached, and the resin laminate obtained in the example was rotated at 20,000 rpm and a conveying speed of 900 mm. The cutting conditions were subjected to cutting, and the cross-section was observed under a microscope. It was observed that the cut profile (chipping; chipping) was X, and the observed was ○.

[Example 1] (Production of hard resin layer)

Dipentaerythritol hexaacrylate: 85 parts by weight and PMMA: 15 parts by weight Heat-kneaded at 110 ° C, and then 1-hydroxycyclohexyl phenyl ketone: 2.5 parts by weight to obtain a curable resin composition.

Then, using a roller coater, the curable resin composition was cast on the release-treated PET so as to have a thickness of 0.15 mm, and another release-treated PET layer was deposited on the cast curable resin composition. Thereafter, the high-pressure mercury lamp of 30 W/cm was used to harden it at a cumulative exposure amount of 4000 mJ/cm ² , and all of the release-treated PET was peeled off to obtain a sheet-like hard resin layer having a specific thickness. The tensile modulus and the total light transmittance were measured for the obtained hard resin layer. The results are shown in Table 1.

(Production of resin laminate)

As a base material layer, a polycarbonate (manufactured by Teijin Co., Ltd., PC-1151, 200 mm × 200 mm × thickness: 0.5 mm (t1)), a countercurrent cation-based photocurable adhesive (manufactured by Kyoritsu Chemical Co., Ltd.) was applied to make a thickness. After the thickness was 5 μm, the hard resin layer obtained above was bonded to the entire surface of one side of the polycarbonate, and after pressing, ultraviolet rays were irradiated from both surfaces at a ratio of 500 mJ/cm ² to a metal halide lamp to obtain a resin laminate. The scratch hardness and workability of the obtained resin laminate were evaluated. The results of the thickness (t ₂ ) of the hard resin layer, the thickness ratio (t ₁ /t ₂ ), and the scratch hardness at this time are shown in Table 1.

[Embodiment 2]

A hard resin layer and a resin laminate were obtained in the same manner as in Example 1 except that the blending composition was the weight ratio shown in Table 1. The evaluation results of the combined molded articles are shown in Table 1.

[Synthesis Example 1]

Into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 400 ml of 2-propanol (IPA) was charged as a solvent and a 5% aqueous solution of tetramethylammonium hydroxide (aqueous solution of TMAH) was used as an alkaline catalyst. Into the dropping funnel, 126.9 g of IPA 150 ml and 3-methylpropenyloxypropyltrimethoxydecane (MTMS: SZ-6030, manufactured by Toray Silicon Co., Ltd.) were placed, and while stirring the reaction vessel, the MTMS was dropped for 30 minutes. IPA solution. After the MTMS was dropped, it was stirred without heating for 2 hours. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in toluene (500 ml). The reaction solution was washed with saturated brine to neutrality, and then dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 86 g of a cage sesquiterpoxypropane compound having a methacryl fluorenyl group on all of the ruthenium atoms. The sesquiterpene oxide is a colorless viscous liquid which is soluble in various organic solvents.

[Example 3]

The cage type sesquiterpoxide compound having a methacryl fluorenyl group on all of the ruthenium atoms obtained in the above Synthesis Example 1 was mixed: 25 parts by weight, dipentaerythritol hexaacrylate: 40 parts by weight, dicyclopentanyl diacrylate: 30 The transparent curable resin composition was obtained in a weight ratio of 1:5 parts by weight of the urethane acrylate oligomer and 1.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator.

Then, a hard resin layer was obtained in the same manner as in Example 1, and a resin laminate was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

[Examples 4 to 9 and Comparative Examples 1 to 4]

The composition of the blending is in addition to the weight ratio indicated in Table 1, A hard resin layer and a resin laminate were obtained in the same manner as in Example 1. The evaluation results of the combined molded articles are shown in Table 1. Further, in Comparative Example 1, since the hard resin layer was large and depressed, it was impossible to determine the flaw.

The abbreviations in the table are as follows.

A: Compound obtained in Synthesis Example 1

B: dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)

C: Trimethylolpropane trimethacrylate (Light Ester TMP, manufactured by Kyoeisha Chemical Co., Ltd.)

D: pentaerythritol triacrylate (Light Ester PE-3A manufactured by Kyoeisha Chemical Co., Ltd.)

E: caprolactone-modified dipentaerythritol hexaacrylate 1 (KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd.)

F: caprolactone-modified dipentaerythritol hexaacrylate 2 (KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd.)

G: Dicyclopentyl diacrylate (Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)

H: Dicyclopentyl dimethacrylate (NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.)

I: PMMA (PARAPET LW manufactured by Kuraray Co., Ltd.: weight average molecular weight of about 34,000)

J: Amino acrylate acrylate oligomer 1 (UF-503 manufactured by Kyoeisha Chemical Co., Ltd.: number average molecular weight of about 8800)

K: urethane acrylate oligomer 2 (NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.: number average molecular weight: about 1100)

L: 1-hydroxycyclohexyl phenyl ketone (polymerization initiator, Japan BASF) System IRGACURE184)

1‧‧‧hard resin layer

2‧‧‧Bonded layer

3‧‧‧Substrate layer

4‧‧‧Printing layer

Claims (8)

A resin laminate having a three-dimensional crosslinked structure and having a thickness of 25 μm or more and 250 μm or less, which is formed of a curable resin composition containing a polyfunctional (meth)acrylic monomer as an essential component. And a base material layer composed of a single layer of a thermoplastic resin or a plurality of layers of two or more layers, wherein the hard resin layer has a tensile modulus of 2,000 to 4,000 MPa alone and a total light transmittance of 90% or more and the total thickness t of the thickness of the base layer ₁ and a hard resin layer is t ₂ ratio (t ₁ / t ₂₎ is 0.25 or more 10 or less, scratch hardness Bill Bam resin laminate 20kg / mm ² or more 700kg /mm ² or less. The resin laminate according to the first aspect of the invention, wherein the number of functional groups of the (meth)acrylic monomer in the curable resin composition forming the hard resin layer is 4 or more, which is a curable resin composition. The solid content contains a ratio of 40 g or more per 100 g. The resin laminate according to claim 1 or 2, wherein the hard resin layer and the substrate layer are laminated via an adhesive layer. The resin laminate according to claim 3, wherein the adhesive layer comprises an adhesive bond selected from the group consisting of an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive. One or two or more of the group. The resin laminate according to claim 1 or 2, wherein the hard resin layer and the thermoplastic resin layer are laminated via an easy-adhesion layer. The resin laminate according to the first or second aspect of the invention, wherein the sturdy resin composition forming the hard resin layer contains a plurality of officials The energy-based (meth)acrylic monomer is a structure having a cage sesquiterpene alkane. The resin laminate according to claim 6, wherein the polyfunctional (meth)acrylic monomer having a cage sesquiterpene structure is represented by the following formula (1): (R ¹ SiO _3/2 ) _n (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1) wherein R ¹ to R ⁶ represent an alkyl group having 1 to 6 carbon atoms a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group or a group having an oxirane ring, which may be the same group or may contain a different group. 1) has at least two (meth)acrylic groups, and n, m, and l are average values, n is a number from 6 to 14, m is a number from 0 to 4, and l is a number from 0 to 4, and satisfies m≦1. The resin laminate according to claim 1 or 2, wherein a hard resin layer is provided on both front and back sides of the base material layer.